CN1286715A - Method of treating resin or organic compound, or waste plastics contg. them - Google Patents
Method of treating resin or organic compound, or waste plastics contg. them Download PDFInfo
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- CN1286715A CN1286715A CN99801646A CN99801646A CN1286715A CN 1286715 A CN1286715 A CN 1286715A CN 99801646 A CN99801646 A CN 99801646A CN 99801646 A CN99801646 A CN 99801646A CN 1286715 A CN1286715 A CN 1286715A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/008—Composition or distribution of the charge
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/02—Making special pig-iron, e.g. by applying additives, e.g. oxides of other metals
- C21B5/023—Injection of the additives into the melting part
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Sustainable Development (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Thermal Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Coke Industry (AREA)
- Industrial Gases (AREA)
- Manufacture Of Iron (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method of treating resin or organic compound, or waste plastics containing them, wherein resin, or organic compound, or waste plastics containing them is partly burned in a blast furnace and the remaining portion is pyrolyzed in a coke oven.
Description
Technical field
Organic compound such as resins such as polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polybiphenyl are discharged as industrial waste or by the general refuse that family collects every year in a large number.Below these materials be called contain resin or organic compound or both plastic waste (are called for short: plastic waste).Plastic waste discharges 4,000,000 tons as industrial waste every year approximately, discharges 4,000,000 tons approximately every year as general refuse.
The present invention relates to the Recycling Technology of Plastic Wastes treatment process.
Background technology
As the method for recycling processing plastic waste, great majority were the methods that adopt burning, landfill disposal in the past.During burning disposal,, roasting kiln is damaged, and when being chloride plastic waste, the problem that chlorine is arranged in the emission gases can occurs handling owing to produce a large amount of heats.Plastic waste can not in the insufficient while of landfill, can cause a large amount of carrying capacities of environment by the bacterial degradation in the soil.Therefore, the needs employing is a kind of does not burn.Landfill disposal is considered the recirculating technique of environment.As the method for recycling that does not burn, except that utilizing again, also have gas that thermolysis is obtained and the method that oil content acts as a fuel and chemical feedstocks utilizes again at present as plastic raw materials.
In gas that thermolysis is obtained and the method that oil content acts as a fuel or chemical feedstocks utilizes again, one of manufacturing process of known iron and steel---in blast furnace, utilize the method (special public clear 51-33493) of plastic waste as reductive agent, recently, for reaching higher efficient, in the middle of various exploitations are being tested.(for example, the spy opens flat 9-170009, spy and opens that flat 9-137926, spy open flat 9-178130, the spy opens flat 9-202907, patent the 2765535th)
When plastic waste is handled in blast furnace, must consider owing to spray into a large amount of plastic waste to cause blast furnace productivity to reduce, and the chlorine that must sneak in the plastic waste.
That is to say that 1 ton of molten iron of every manufacturing if pack into above the plastic waste of 10kg to blast furnace, will cause the inerting of the State of Blast Furnace heart, thereby the productivity of making the pig iron is significantly reduced.Thereby former per 1 ton of molten iron is handled 10kg at most in blast furnace.In addition, polyvinyl chloride, polyvinylidene dichloride, polybiphenyl contain chlorine, the occasion that the occasion of industry plastic waste is on average sneaked into tens of wt%, general plastic waste on average sneak into tens of wt% degree chlorine, even through select handling, in industrial plastic waste, general plastic waste, also can on average sneak into several wt% degree chlorine.When directly packing this plastic waste into blast furnace, chlorine in the plastic waste is because thermolysis forms chlorine-containing gas, for example chlorine, hydrogenchloride cause blast furnace iron sheet burn into blast furnace cooling gradient water cooler burn into blast furnace furnace roof exhaust equipment burn into blast furnace furnace roof generating set corrosive problem.Therefore, after removing chloride plastic waste in advance or removing chlorine in the plastic waste, reinstall blast furnace.
Known (special public clear 49-10321, spy open clear 59-120682) very early, attempting considering the charging method etc. of coke strenth, various more effective exploitation of carrying out Treatment of Waste Plastics as the method for one of iron and steel manufacturing process heating and decomposition treatment plastic waste in coke-fired furnace recently.(for example the spy opens flat 8-157834 etc.) coke-fired furnace is the equipment of destructive distillation coal, and is same, also is the recirculation unit that can the destructive distillation plastic waste obtains combustion gas, tar, coke.
In coke-fired furnace during treatment of waste plastics, identical when handling with blast furnace, must consider that the coke-fired furnace productivity that is caused by plastic waste reduces and plastic waste in the chlorine that must sneak into.
At present, mix when packing coke-fired furnace into,, will cause coke quality sharply to descend if pack into above 10kg with respect to per 1 ton of coal with coal.Therefore, theoretical prediction coal per ton can be handled 10kg in coke-fired furnace, in the coke-fired furnace of the plastic waste of chloride about 3-5wt% directly must being packed into, possibility residual chlorine in the coke, in addition, the problem that not only has the chlorine-containing gas corrosion exhaust-duct that generates by thermolysis, and existence is as the tar of by product, sneak into the problem of chlorine-containing gas in the coke-fired furnace gas, so must opening as described in the flat 7-216361 communique usually as the spy when packing coke-fired furnace into, thermolysis in advance reinstalls after removing dechlorination, or open as described in the flat 8-259955 communique in advance as the spy and to remove chlorine-containing resins by proportion separation etc. and again plastic waste is packed in the coke-fired furnace, do not reattempted in coke-fired furnace at present and handled.
In the method for in blast furnace plastic waste being utilized as reductive agent as one of iron and steel manufacturing process, the plastic waste amount that is sprayed to blast furnace by the air port is limitary, considers the reduction of blast furnace productivity in addition, even capacity is 4000m
3Large blast furnace because average porductivity coefficient is 2t/m
3Even, spray into to blast furnace to greatest extent, the annual plastic waste that also only can handle 30,000 tons, this can not adapt to the social demand that makes annual a large amount of plastic waste recirculation of discharging.In addition, for the blast furnace of packing into after removing chloride plastic waste in advance or removing chlorine in the plastic waste, cause operation to become complicated, processing costs increases.Usually after the plastic waste of being collected by the city centre is handled through magnetic classification, aluminium pot classification etc. in advance, contain the chlorine of 3-5wt% approximately.This mainly is owing to the polyvinyl chloride that contains 6-10wt% in the plastic waste causes.If the content of chlorine is not below 0.5wt% in the blast furnace usually, the chlorine-containing gas in the blast furnace can cause the corrosive problem.Therefore, adopt to be heated to about 300 degree and in advance chlorine to be removed with the form of chlorine-containing gas, or, for example be divided into light plastic and heavy plastics, pack into the treatment process of blast furnace of the light plastic that cl content is less by centrifuge separator by the proportion separation.But, with the plastic waste collected all in the dechlorination device dechlorination need very large expense, in addition, it also is very difficult technically that chlorine is taken off 0.5wt% by 3-5wt%, so generally do not adopt.Not as adopting proportion to separate, for example be divided into light plastic and heavy plastics, then pack into the treatment process of blast furnace of the light plastic that cl content is less only by centrifuge separator.But,, also have problems even adopt this method.With the centrifuge separator is that example is explained.Plastic waste 100kg behind the general impurity (vinylchlorid 10kg wherein will be removed, chlorine weight is 5kg) be impossible carry out ideal to separate in centrifuge separator, being that 0% material reaches 90kg as the cl content of lightweight part promptly, is that the material of 50% (cl content of polyvinyl chloride is about 57wt%) reaches 10kg as the cl content of heavy part.Present situation is that the cl content that separation obtains as the lightweight part is the material 50kg of 0.5wt%, as the cl content of heavy part 9.5% material 50kg, even or to separate the cl content also only obtain as the lightweight part under optimal condition be 0.5% material 70kg, as the cl content of heavy part 15.5% material 30kg.At this moment, the plastic waste of chloride 9.5-15.5wt% is carried out dechlorination, and to be reduced to cl content be to be impossible below the 0.5wt%, isolated heavy part plastic waste (30-50% of the plastic waste before being equivalent to separate) can only be as residue treatment, for example landfill disposal.During as residue treatment, having more than is that residue per ton needs about 30,000 yen handling, and this expression Recycling Technology of Plastic Wastes rate is very low after all, the recycling processing method of the social demand of the so-called recirculation of adaptation of can not saying so.
In coke-fired furnace, utilize the method for plastic waste as one of iron and steel manufacturing process, as mentioned above owing to have realized that thermal degradation reinstalls after removing dechlorination in advance, or in the coke-fired furnace of after removing chlorine-containing resins by proportion separation etc. in advance, again plastic waste being packed into, therefore in actually operating, still do not attempt in coke-fired furnace, handling.Remove in advance the problem of dechlorination, have great number dechlorination expense, great number heavy Treatment of Waste Plastics expense, problem that recirculation rate is low as mentioned above, so can not be used as plastic waste recirculation in blast furnace.
Even reinstall after removing dechlorination, to handle even plastic waste is incorporated with to greatest extent in the coke-fired furnace of 100 furnace chambers, also only can handle 10,000 tons every year, and this can not adapt to the social demand of a large amount of plastic waste recirculation that will give off every year.
Invention is described
The invention provides the method that solves problem in the prior art, not only provide a kind of and in the steel ironworker's of making preface, do not need unnecessary facility investment, former ability by the blast furnace treatment of waste plastics is enlarged as the processing power of making in ironworker's preface, in coke-fired furnace, handle residue, with the method for plastic waste as gas, tar, the recirculation of coke composition, a kind of minimizing also is provided or omits the burden that to carry out the dechlorination operation in the past in advance to plastic waste, improve the treatment process of recirculation rate simultaneously.Its purport is: need not remove chlorine in the plastic waste in advance and directly pack in the thermal decomposition furnace, the thermolysis gas that comprises chlorine-containing gas is contacted with ammoniacal liquor,, as the basis this method be combined with the Treatment of Waste Plastics that adopts blast furnace with this method.If adopt coke-fired furnace, also be suitable owing to can utilize the ammoniacal liquor that produces by coal as thermal decomposition furnace.But the present invention has more than and is confined to coke-fired furnace, as long as thermal decomposition furnace and ammonia source are arranged, and blast furnace can be realized.When utilizing coke-fired furnace as thermal decomposition furnace, the inventor has found 3 embodiments of following explanation.
First kind of mode is for example to utilize proportion to separate chloride plastic waste is divided into chloride many material and chloride few material, chloride many materials are packed into carry out thermal decomposition process in the coke-fired furnace, chloride few plastic waste blast furnace of packing into is carried out the method (Fig. 3 A) of thermal decomposition process.
The second way is to handle at the blast furnace that the part of plastic waste carried out in advance pack into after dechlorination is handled, and part or all of remainder do not carried out the method (Fig. 3 B) that the coke-fired furnace of directly packing into is handled in dechlorination in advance.
The third mode is that the plastic waste of the dechlorination that do not eliminate the in advance blast furnace of packing in the cl concn allowed band is handled, and part or all of remainder still do not removed the method (Fig. 3 C) that dechlorination is directly packed into and handled in the blast furnace in advance.
The simple declaration of drawing
Fig. 1 is the schema of treatment of waste plastics method of the present invention.Among Fig. 1, the 1st, the sorting equipment of plastic waste, the 2nd, coke-fired furnace, the 3rd, blast furnace, the 4th, the plastic waste of vinyl-chloride-containing, the 5th, contain the plastic waste of a large amount of vinylchlorid, the 6th, vinyl-chloride-containing plastic waste seldom, the 7th, coke-fired furnace gas, the 8th, coke, the 9th, installation for blast furnace gas, the 10th, molten iron.
Fig. 2 is the raw material schema of expression plastic waste when using in iron and steel manufacturing (blast furnace, coke-fired furnace).
Fig. 3 A-3C is the figure of the concrete processing mode of expression the present invention.
The preferred forms of invention
The method that the chlorine-containing gas that produces when at first, the inventor finds to make the employing thermal decomposition furnace carry out thermolysis contacts with ammoniacal liquor is very economical.Discovery can adopt the coke-fired furnace of one of the steel ironworker's of making preface as thermal decomposition furnace, the at this moment unnecessary dechlorination that removes from plastic waste in advance.With blast furnace and coke-fired furnace combination, can realize not carrying out in advance dechlorination and handle treatment of waste plastics (Fig. 3 A) in blast furnace on this basis, can save total dechlorination funds (Fig. 3 B), perhaps can reduce chlorine blast furnace corrosive problem (Fig. 3 C).
At first, the inventor has carried out deep research to the plastic waste that destructive distillation in coke-fired furnace contains chlorine.When the coking chamber destructive distillation coal of coke-fired furnace, beyond the coke-fired furnace gas decoking oil that produces, also contain water, ammonia, after coke-fired furnace gas is discharged from coke-fired furnace, by cooling off with ammoniacal liquor (ammoniacal liquor that coal is produced stores, circulates) flushing, with the coke-fired furnace gas and the tar separation of the gas that acts as a fuel, water in the coke-fired furnace and ammonia formation ammoniacal liquor recycle simultaneously.Therefore, the inventor considers because so long as will there be ammonia in coke-fired furnace in coke-fired furnace gas, even generated chlorine-containing gas during thermolysis, also can form ammonium chloride and make it to become harmless, so carried out following detailed research.
When in the coking chamber of coke-fired furnace, carrying out destructive distillation, think chlorine in resin or the organism 250 ℃～1300 ℃ decomposition, also have in coke as inorganics residual may.But plastic containing chlorine is during with the coal destructive distillation, confirms that chlorine transfers to gas phase more than 90%, and staying as residue and residual in the coal is below 10%.
In addition, if chlorine-containing gas is trapped in the coking chamber, the possibility that leakage is arranged when extruding coke, the chlorine-containing gas of gas phase rises in the coking chamber of coke-fired furnace but affirmation is divided a word with a hyphen at the end of a line, arrive the furnace roof space on the coal top of being packed into, when extruding under 1100 ℃ of environment through after the destructive distillation, in stove, almost do not have residual.
The inventor has carried out concentrated research, learn because the chlorine-containing gas that the plastic containing chlorine thermolysis produces is mordant gas, if hydrogenchloride is directly discharged from exhaust system, probably can corrode the pipeline of exhaust system, but chlorine-containing gas mixed the gas that obtains with the coke-fired furnace gas that contains ammonia and import ventage by the upcast of coke-fired furnace, be cooled to 80 ℃ with water coolant (ammoniacal liquor) flushing, it is shocking that the chlorine-containing gas that contains in the above-mentioned gas most is hunted down, the coke-fired furnace gas after the flushing contains chlorine hardly.
This is to form ammonium chloride owing to derive from the ammonia and the chlorine-containing gas of coal by flushing, is dissolved in the ammoniacal liquor, separates with coke-fired furnace gas.
Contain tar in the ammoniacal liquor, it is separated by decant, separate the ammoniacal liquor interim storage in ammonia water tank usually remove behind the tar, be rejected to outside the system, residual be used for flushing once more with the ratio of 1 ton of coke 100～200kg ammoniacal liquor.If repeatable operation, then ammonium chloride is accumulated in the ammoniacal liquor, probably can exceed solubleness sooner or later.The ammonium chloride that the ammoniacal liquor that is used for washing is residual to have last flushing to be caught, but by the destructive distillation coal, the moisture of being emitted by coal also are equivalent to 1 ton of coke 100～200kg (about 5500mol～11000mol).This is owing to originally just contained 9% the moisture of having an appointment in coal, has in addition produced about 3% moisture by reaction.For example emit 160kg water at 1 ton of coke of manufacturing, the solubleness of ammonium chloride is " 37.2g/100g water, 20 ℃ ", can be allowed the ammonium chloride of about 1100mol (=160000 * 0.372 ÷ 53.4) by the per 1 ton of coke of molecular weight 53.4 calculating of ammonium chloride.When being equivalent to its plastic containing chlorine 10kg of 1% for 1 ton of coal interpolation, even half of this weight is polyvinyl chloride, the chlorine of generation also (is scaled 80mol by HCl, presses Cl nothing but 80mol
2Be scaled 40mol), the amount of moisture that produces during the destructive distillation coal be enough to make chlorine that plastic containing chlorine produces as chloride leach in water.Therefore, it is saturated not worry that flushing can be chlorinated ammonium with ammoniacal liquor.
As mentioned above, at first the inventor has carried out concentrated research for the plastic waste that contains chlorine with the coke-fired furnace destructive distillation, even find 1. will to contain the resin of chlorine or organic compound with coal destructive distillation in coke-fired furnace, can not remain in the coke yet, 2. when 250 ℃～1300 ℃ destructive distillation, chlorine shifts to gas phase, 3. transferring to the chlorine major part of gas phase is caught by ammoniacal liquor as ammonium chloride when washing with ammoniacal liquor, even 4. recycle ammoniacal liquor, owing to also produce moisture during the dry distillation of coal, it is saturated that flushing can not be chlorinated ammonium with ammoniacal liquor, found that making one of ironworker's preface as iron and steel industry does not need to remove in advance dechlorination in coke-fired furnace, the chlorine-containing gas that produces when not needing thermolysis is handled especially, just can make the plastic waste that contains chlorine become harmless.
Secondly, the inventor is for the treatment capacity that enlarges plastic waste in steel plant process, and reduce or omit before must the step of the prior dechlorination of plastic waste be improved the treatment process of recirculation rate and carry out concentrated research.This is very significant for making in the iron process kind that increases plastic waste, making the production stabilization of making in the iron process.
In the routine operation in blast furnace, the dust coal that sprays into by agglomerate, coke, air port as raw material, per 1 ton of molten iron is sneaked into the chlorine of about 300g, if this amount increases considerably, can cause the etching problem of blast furnace iron sheet, gradient water cooler, furnace roof exhaust-duct, furnace roof generating set etc.When spraying into plastic waste 10kg with respect to per 1 ton of molten iron by the air port, if the content of chlorine is not reduced to below 0.5%, it is remarkable that above-mentioned etching problem can become.
Therefore, the inventor finds by corresponding to the content of chlorine plastic waste being classified in advance, the treatment combination that processing that the coke-fired furnace that does not need in advance dechlorination to handle employing carries out and employing are carried out the conditional blast furnace of chlorine add-on, not only can enlarge the treatment capacity of the plastic waste in the iron and steel production, and must be before can omitting to the step of the prior dechlorination of plastic waste, the high plastic waste recirculation of cl content that can only landfill before making has improved recirculation rate.
That is to say, the plastic waste of collecting is divided into many few with cl content of cl content, few (preferred cl content is the material below 0.5%) of cl content in blast furnace as reductive agent recirculation, what cl content was many does not need in advance except that dechlorination, carry out destructive distillation and handle in coke-fired furnace, the dechlorination step that the expense of can omitting is very high reduces the chlorine of blast furnace and loads, increase processing power, improve recirculation rate.According to the present invention that the inventor finds, when cl content is very high in predicting the plastic waste that is recovered, be very economical and practical recycling processing method.
In addition, the inventor finds can to enlarge the treatment capacity of plastic waste in the steel plant process by adopting processing that the coke-fired furnace that do not need dechlorination to handle in advance carries out and employing to the treatment combination that the conditional blast furnace of chlorine add-on carries out.That is to say,, handle remainder corresponding to the collection situation with coke-fired furnace again by handle manageable amount with blast furnace; Or handle manageable amount with coke-fired furnace, handle remainder corresponding to the collection situation with blast furnace again, not only can enlarge the Recycling Technology of Plastic Wastes treatment capacity, improve recirculation rate, and any one is produced when unstable in blast furnace, coke-fired furnace, can reduce the Treatment of Waste Plastics amount of producing unsettled stove, increase the recycling processing amount of another kind of stove, make the production stabilization.When adopting this method, with blast furnace (the about 4000m that makes 3,000,000 tons of molten iron every year
3, porductivity coefficient is 2) describe for example.At this moment, necessary coke is about 1,200,000 tons, considers the quality of coke, if per 1 ton of coke disposal plastic waste 10kg then may handle 1.2 ten thousand tons plastic waste.On this, add the plastic waste 10kg that is equivalent to 1 ton of molten iron that handles with blast furnace, can treatable maximum add up to 4.2 ten thousand tons, treatment capacity is increased considerably.
And, the inventor studies the permission situation of chlorine in the blast furnace, found that for the plastic waste of collecting and to have removed dechlorination in advance, also do not adopted, can enlarge the treatment process of making the treatment capacity in the iron process corresponding to the content of chlorine step by separation plastics such as proportion separation.
Convert by chlorine in the plastic waste that reclaims respectively by family and contain the chlorine of 5～10wt%.Even after reclaiming by being used to remove the air classification of impurity etc., still containing 3% the chlorine of having an appointment.Can corrode blast furnace when spraying into plastic waste 10kg with respect to per 1 ton of molten iron from the air port before considering, carrying out dechlorination in advance, to handle the degree that the content that makes chlorine is reduced to 0.5wt% be necessary.But the etching problem that found that blast furnace of inventor research is not the problem that the content of chlorine in the plastic waste of handling with blast furnace causes, but the problem that the total amount of chlorine add-on causes in per 1 ton of molten iron.In the routine operation of discovery in blast furnace, the dust coal that is sprayed into by agglomerate, coke, air port as raw material is sneaked into the chlorine of about 300g with respect to 1 ton of molten iron, if surpass 350g with respect to 1 ton of molten iron, then etching problem is serious.Therefore, when discovery sprays into 10kg with respect to per 1 ton of molten iron by the air port, it is necessary by prior dechlorination the content of chlorine being reduced to 0.5wt%, but is limit when packing plastic waste in blast furnace with 1.7kg with respect to per 1 ton of molten iron, does not need prior dechlorination for the plastic waste that contains the 3wt% chlorine of having an appointment.This not only can save about 30,000 tons of plastic waste are carried out dechlorination necessary 1,000,000,000 yen～2,000,000,000 yen and the facility investment of carrying out dechlorination in advance in advance, and is very economical.
But though adopt this method can omit dechlorination, because 1 blast furnace can only be handled 5000 tons at most every year, for the processing of the annual 1500 tons of plastic waste that discharge of per 100,000 resident populations, processing power is also not enough.
Therefore, the inventor has found by setting the blast furnace Intake Quantity higher limit when not needing in advance to carry out dechlorination and handling, with the treatment combination that adopts the prior coke-fired furnace that does not need dechlorination to handle to carry out, must be before can omitting to the step of the prior dechlorination of plastic waste, need not adopt by the step corresponding to the cl content separating plastic such as proportion separation yet, can realize enlarging the treatment process of making the treatment capacity in the iron process.
If consider the quality of coke, present limit is per 1 ton of coke disposal plastic waste 10kg.At this moment, for the blast furnace of making 3,000,000 tons of molten iron every year, necessary coke is about 1,200,000 tons, therefore may handle 1.2 ten thousand tons plastic waste.On this, add and to make the blast furnace of 3,000,000 tons of molten iron (about 4000m every year
3, porductivity coefficient is about 2) can treatable amount 5000 tons, 1.7 ten thousand tons altogether of possible recycling processing plastic waste.
The inventor has finished the present invention based on above-mentioned research.Purport of the present invention is:
(1) contains the treatment process of resin or organic compound or both plastic waste, it is characterized in that the part that will contain resin or organic compound or both plastic waste handles as reductive agent in blast furnace, to the remaining all or part of thermal decomposition process of carrying out, the gas that thermolysis is produced contacts with ammoniacal liquor.
(2) as (1) the described treatment process that contains resin or organic compound or both plastic waste, it is characterized in that ammoniacal liquor produces when the destructive distillation coal.
(3) contain the treatment process of resin or organic compound or both plastic waste, a part that it is characterized in that containing resin or organic compound or both plastic waste is handled as reductive agent in blast furnace, all or part ofly carries out thermal decomposition process with coke-fired furnace to remaining.
(4) contain the treatment process of resin or organic compound or both plastic waste, it is characterized in that to contain resin or organic compound or both plastic waste and be divided into cl content many material and the few material of cl content, in blast furnace, handle the few material of cl content, in coke-fired furnace, the high material of cl content is heat-treated.
(5), it is characterized in that will contain resin or organic compound or both plastic waste by the proportion separation is divided into cl content many material and the few material of cl content as (4) the described treatment process that contains resin or organic compound or both plastic waste.
(6) contain resin or organic compound or both Treatment of Waste Plastics methods, it is characterized in that to contain resin or organic compound or both plastic waste and be divided into above material of cl content average out to 0.5wt% and the following material of cl content average out to 0.5wt%, in blast furnace, handle the material below the cl content average out to 0.5wt%, the material more than the cl content average out to 0.5wt% is carried out thermal decomposition process in coke-fired furnace.
(7) contain resin or organic compound or both Treatment of Waste Plastics methods, after it is characterized in that to contain resin or organic compound or both plastic waste parts and carrying out dechlorination in advance and handle, in blast furnace, handle as reductive agent, for the remaining all or part of dechlorination processing of not carrying out in advance, carry out thermal decomposition process simultaneously with coke-fired furnace.
(8) as (7) the described treatment process that contains resin or organic compound or both plastic waste, it is characterized in that containing resin or organic compound or both plastic waste parts and carry out dechlorination in advance and handle the content of chlorine is reached below the 0.5wt%, in blast furnace, handle then as reductive agent.
(9) as (8) the described treatment process that contains resin or organic compound or both plastic waste, it is characterized in that to contain resin or organic compound or both plastic waste and carry out dechlorination in advance and handle cl content is reached below the 0.5wt%, handle the product of the above-mentioned prior processing of 0.5kg～10kg then with respect to 1 ton of molten iron with blast furnace.
(10) contain the treatment process of resin or organic compound or both plastic waste, it is characterized in that containing resin or organic compound or both plastic waste parts and directly do not handle as reductive agent in blast furnace except that dechlorination in advance, the remaining all or part of dechlorination that do not remove in advance carries out thermal decomposition process in coke-fired furnace.
(11) as (10) the described treatment process that contains resin or organic compound or both plastic waste, it is characterized in that with per 1 ton of molten iron 0.5kg as lower limit, with the blast furnace treatment capacity of considering the chlorine permissibility is the upper limit, will contain resin or organic compound or both plastic waste and not remove dechlorination in advance and directly handle as reductive agent in blast furnace.
(12), it is characterized in that not removing dechlorination in advance and directly in blast furnace, handling containing resin or organic compound or both plastic waste below the above 1.7kg of 0.5kg with respect to 1 ton of molten iron as (11) the described treatment process that contains resin or organic compound or both plastic waste.
According to the present invention,,, have to make and handle the effect that reaches stabilization even when the production of recycling processing equipment is unstable, can carry out recycling processing with other system for the amount of the plastic waste of collecting.
In addition, according to the present invention,, also can handle and recirculation rate does not reduce even the content of chlorine changes in the plastic waste of collecting.That is to say, before can making most of as residue by the effective recirculation of chloride heavy plastic waste of landfill disposal.
And, with in making the iron process before only the occasion that plastic waste carries out recycling processing is compared raising recirculation rate, recirculation volume that can be rapid with blast furnace.
Plastic waste that can not recirculation before can making carries out material recirculation as reductive agent or as tar, coal gas etc.With the most of high calorie reduction decomposition gases such as hydrogen, methane, ethane, propane that form of coke-fired furnace pyrolysated plastic waste, be contained in the coke-fired furnace gas, can be used as reusing of energy source by recovery.In addition, Can Yu carbon is reused at blast furnace as the part of coke.The total figure of recirculation of the present invention as shown in Figure 2.
In Fig. 2; the plastic waste that plastics such as the container of uses such as family, packing produce is through removing impurity, subtracting in the material that is contained, preserves after the pre-treatment such as holding processing, dechlorination processing, granulating; its part adopts blast furnace to handle according to the present invention after handle the blast furnace raw material stokehold.Molten iron by the blast furnace manufacturing is used for purposes such as buildings, bridge, tame electrical article, office machine after refining, calendering, processing such as electroplate, spray paint.The blast-furnace slag that is produced by blast furnace is used for high energy building materials, ceramic fiber, cement, road etc. as water muck slag, slow cooling slag etc.Installation for blast furnace gas (BFG) can be used for coke-fired furnace in addition.A pretreated plastic waste part still with the coal of storage equally through the coke raw materials pretreatment, in coke-fired furnace, handle through destructive distillation (cokeization), make coke.This coke uses in blast furnace.In addition, in coke-fired furnace, produce and be used for Essential Chemistry goods, synthetic paper, coating etc. such as hydrogen, ammonia, carbon fiber, ethene in chemical plant by oiled tar, light oil, BTX, phenol, naphthalene etc., be used for the manufacturing of plastics class raw material and even plastics group, recirculation is used for the plastics of family etc.The coke-fired furnace gas (COG) that is obtained by coke-fired furnace gasification is used for power station or refining of cast-iron etc. through gas purification factory, simultaneously by the modification to methyl alcohol etc., is used for the manufacturing of hydrogen, ammonia, carbon fiber, ethene etc. in chemical plant with thiamines.
At first describe for the method for in blast furnace, plastic waste being handled as reductive agent.If contain plastic containing chlorine or impurity in the industry plastic waste, can distinguish mutually with the material that does not contain, collect from discharging factory respectively.Can concentrate in conjunction with the carrying capacity of housing apparatus according to size, shape.
For the plastic garbage that discharges respectively by family as general plastic waste, do not fire rubbish, at first collect for the first time by commune.The material that concentrates on the stock yard (stockyard) of commune is transported in the treatment facility of autonomous community by the private enterprise of the plastic garbage recirculation of doing evil through another person.At this moment, plastic material and impurity can not be concentrated respectively.
In order to make the industrial plastic waste that is transported in the autonomous community treatment facility, general plastic waste be in proper state when packing blast furnace into, carry out pre-treatment earlier.
When being industrial plastic waste, when it is not chloride solid plastic waste, with its pulverizing-remove impurity-fine powder broken (10mm is following), the particulate matter of using as blast furnace.When containing chlorine, utilize the gravitational separation device of difference in specific gravity (plastic containing chlorine is more than 1, and not chloride plastics such as PE, PP, PS are below 1) to separate, be divided into high plastics of cl content and the low plastics of cl content in fine powder broken back use.The cl content that separation obtains reaches the following low plastics of cl content of 0.5wt% becomes the particulate matter that blast furnace is used.On the other hand, with made the particle of 10～70mm in the past by the high plastics of the cl content of landfill disposal, handle with coke-fired furnace, be not subjected to the influence of the utilization rate of raw materials of gravity separation machine, the plastic waste of removing behind the impurity almost 100% can recirculation.
When it is general plastic waste, collection mode difference according to each village, city, foreign matter content also differs widely, and it is the combustiblematerials at center that the average group of various plastics becomes with plastics: 75% (wherein chlorine is 5～10%), magneticmetal: aluminium 5%: inorganic components such as glass 2%: 8% (wherein 5% is the inorganic components in the combustible component), moisture: 10%.In order to be made into the particulate material that is used for the blast furnace reductive agent, chlorine is reached below 0.5%, ash content reaches below 5%, must carry out broken bag-magnetic separation-remove impurity-fine powder broken-step of gravity separation-dehydration-drying-granulation.At this moment, according to the proper property of gravity separation machine, the broken plastics of fine powder (10～20mm, shape the is indefinite) 50～70wt% that puts in the gravity separation machine can be separated as the plastics (cl content is that 0.5wt% is following) as the blast furnace reductive agent.
Reach dechlorination method below the 0.5wt% as separate the cl content make the plastic waste that sprays into from blast-furnace tuyere without proportion, be heated to 300 ℃ with resin two-fold mixing roll and can realize (for example the spy opens and puts down 8～No. 120285 communiques) by known.
Because when in blast furnace, causing the amount of chlorine to increase by crude fuel, hydrogenchloride can cause in the stove and the problem of exhaust system corrosion, hinder reaction in furnace, the degree that it is 50g that the amount that the chlorine that is caused by handled plastic waste increases must be controlled at respect to 1 ton of molten iron, therefore implement above-mentioned proportion separation or dechlorination and handle, when in blast furnace, spraying into the plastic waste of about 1.7kg (10/6), because the classification after reclaiming with respect to 1 ton of molten iron, chlorine almost has been reduced to 3%, not necessarily must carry out dechlorination.
Because the reasons such as temperature height of furnace roof portion spray into plastic waste by blast-furnace tuyere.The amount that sprays into plastic waste from the air port is with to spray into dust coal identical, according to decisions such as the air quantity of density, particle diameter and the hotblast stove of avoiding not firing viewpoint that composition causes air permeability difference in the stove, plastic waste, wind speed.For these straying quatities and the plastic waste form that sprays into, because those skilled in the art were just very clear in the past, also have by patent etc. disclosedly, therefore here no longer describe in detail (the flat 8-50715 communique of for example special table, spy open flat 9-170009 communique, spy are opened flat 9-137962 communique, the spy opens flat 9-125113 communique etc.).
As the upper limit of the amount of in blast furnace, packing into,, handle with respect to can pack into the plastic waste of 10kg of 1 ton of molten iron maximum if do not consider the content of chlorine.If surpass this value, will cause the inerting of the stove heart, the result probably hinders blast furnace productivity.On the other hand, if Intake Quantity reaches below the 0.5kg, then do not reach the meaning of recirculation.Spray into the plastic waste 10kg that contains chlorine 0.5wt% with respect to 1 ton of molten iron by the air port in blast furnace, the add-on of chlorine is a 50g/1 ton molten iron.Because usually contained cl concn is 300～350g/1 ton molten iron in the blast furnace that is brought by blast furnace raw material during operation, the ratio of the chlorine add-on of being brought by plastic waste has increased by 20%.This is in the actually operating allowed band, as the higher limit of bringing the amount of chlorine in the blast furnace into.If control bring chlorine in the blast furnace into total amount, utilize blast furnace plastic waste contain cl concn corresponding to Intake Quantity can allow the number %.
The plastic waste of can not handling Wan for the high plastics of the cl content that utilizes blast furnace to be separated or with blast furnace can be that thermal decomposition process stoves such as the partial oxidation furnace of purpose or gas retort carry out pyrolytic decomposition with the gasification by what together be provided with blast furnace.In the reductive environment, if the gasification temperature of plastic waste more than 400 ℃, the stove of any kind all can adopt, and for example also can adopt the CDQ equipment of coke (cooling heat reclaim).
The high-temperature gas that the thermolysis plastic waste generates is at first removed chlorine-containing gas with washings such as alkali, and decomposition gas can be used as industrial chemicals afterwards, high energy gas is utilized industrial.
The plastic waste that contains chlorine carried out the hydrocarbon gas that can obtain carbon, ash content residue and contain chlorine after the thermal decomposition process.Carbon, ash content residue can be used as coke as the reductive agent of blast furnace, except that the hydrocarbon gas of dechlorination except that with coke-fired furnace gas is utilized with raw material as chemical preparations, can also be utilized as the high efficiency ironworks energy of making.The plastic waste of thermal decomposition process is handled by blast furnace and coke-fired furnace combination, and product can be realized very high recirculation rate.
The plastic waste of packing in heat treatment furnace must contain chlorine-containing gas in the gas that produces during thermolysis.As the method that makes it to become harmless, can realize by the spraying plant that ammoniacal liquor is installed in the exhaust-duct.In steel plant process, as the alkali of the high temperature hydrocarbon gas washing usefulness that contains chlorine, the ammoniacal liquor that has coke-fired furnace to produce.Ammoniacal liquor is to absorb the ammonia that is produced by coal in the process of cokeization, with the coke gas cooling (below 80 ℃) of high temperature (about 900 ℃), is purpose with the purification, the round-robin water of spraying.The thermal decomposition process stove is set when coke-fired furnace is set, and by the thermal decomposition furnace expellant gas is partly linked to each other with the upcast of coke-fired furnace, the high temperature hydrocarbon gas that contains chlorine-containing gas contacts with ammonia, and chlorine-containing gas is fixed as ammonium chloride.The amount that per 1 ton of feed coal produces ammonia is 3000～4000g, and when for example handling chloride 5% plastic waste 10kg with respect to 1 ton of coal, the amount that adds chlorine is 500g, has the neutralising capacity more than 6 times.
Coke-fired furnace is ideal stove when plastic waste is carried out thermolysis.The collection of the plastic waste of handling with coke-fired furnace is identical when handling with blast furnace, so no longer explanation.In coke-fired furnace to by the isolating heavy plastic waste of proportion (cl content be 7～30wt%) or the plastic waste that adopts blast furnace to handle not Wan carry out the destructive distillation processing.
When in coke-fired furnace, packing plastic waste into, must select to remove metal species impurity.The plastic waste of collecting holds operation steps by coarse reduction (broken bag)-magnetic separation-remove impurity (non-magnetic substance)-subtract and reaches ash content: below 10%, chlorine: below 30%, more than granularity: 10～70mm, low heat emission amount: the 5000kcal/kg, heavy metal: below 1%.In addition, the high chlorine heavy plastics except that being used as the blast furnace reductive agent remove by washing and deash, heavy metal carries out granulation, can satisfy the above-mentioned prilling process that is used for coke.By compound blast furnace process and the coke method utilized, almost can make plastic waste 100% recirculation.
When packing plastic waste into coke-fired furnace, block plastics are crushed to the granularity of regulation, as charging feedstock.But,, only it is crushed to the granularity of regulation merely because plastic waste reclaims as membranous body, foam, powder after all, can form the big charging feedstock of bulk density small volume, owing to contain too much powder, be difficult to mix in addition, pack into sometimes and can have any problem with the coal of coke raw material.In addition, the plastics that the bulk density small volume is big have the possibility of catching fire near the high temperature coke body of heater, are very difficult to handle.Therefore, by in advance plastic containing chlorine being heated to 80 ℃～190 ℃ temperature, compression in this state, cooling once again makes it to subtract to hold and solidifies.Subtract the coke strenth of the size of holding cured article can be according to its hauling ability, with the mixed performance of coal, with the coal destructive distillation time, the danger of catching fire etc. and suitably set the diameter about preferably approximately 5-10mm.Hold the solidified method as subtracting, can adopt previously used materials such as resin mixing roll or pulverizer, cylinder type well heater.
For example there are the method (spy opens flat 9-157834 communique) of adding in the furnace roof space, the method (spy opens flat 9-132782 communique) of adding in the coking chamber bottom, the prior back charging method (for example the spy opens flat 6-228565 communique) that mixes with coal in the position that plastic waste is packed in coke-fired furnace.When collecting the coking chamber that plastic waste packs into specific, can adopt following method: the gas delivery by rare gas element is discharged in the specific coking chamber with rare gas element by the funnel that stores with quantitative discharging function behind the coke-fired furnace top.When packing into,, preferably under the atmospheric condition of obstruct, carry out, can open the method for the applicant's proposition of the application in the flat 4-41588 communique according to the spy specifically for fear of ejection thermolysis gas, suction atmosphere.The present invention adopts any charging apparatus, the position of packing into, charging method all are effective.
When handling with coke-fired furnace, also a plurality of coking chamber parts of coke-fired furnace can be exclusively used in Recycling Technology of Plastic Wastes, owing at this moment can increase the amount of handling with coke-fired furnace, can further enlarge processing power, the prior dechlorination that when increasing processing power, also can omit plastic waste.Specifically, following method is arranged: several coking chambers of the coke-fired furnace that is made of more than 100 coking chambers are exclusively used in the thermal treatment of plastic waste, with the ammoniacal liquor flushing that the coke furnace gas body and function that contains chlorine-containing gas that produces recycles in coke-fired furnace, the chlorine that makes in the coke-fired furnace to be contained becomes harmless.The reason that can adopt this method is owing to the occasion flushing at coke-fired furnace has at all coking chambers with ammoniacal liquor.Compare with the pyrogenous occasion of coal with plastic containing chlorine, this method to the amount of the plastic containing chlorine of the coking chamber of packing into without limits neither be necessary as the coal in ammonia source, and the temperature of coking chamber also can suitably be set 400～1300 ℃ scope.
In the part coking chamber of coke-fired furnace, plastic waste is carried out thermolysis, during other coking chamber destructive distillation coke, there is no need to worry that the quality of coke reduces with a plurality of coking chambers.
By the way, coke-fired furnace is the device of destructive distillation coal, for the chlorine-containing gas that plastic waste is produced becomes harmless, produces necessary ammonia by coal.This ammonia is partly accepted the flushing of water at upcast, and cooling forms ammoniacal liquor.This ammoniacal liquor is in the common recycle of the riser portions of each coking chamber.
As this process of washing, the method that coke-fired furnace uses before can adopting.Temperature at furnace roof space gas is about 800 ℃, and the hydrogen chloride gas of generation and ammonia are by this furnace roof space, and the upcast that is provided with via coking chamber top imports ventage.Temperature at upcast position gas is about 700 ℃.The material of upcast can use general cast iron, according to occasion consider to up to water to the spray corrosion of pipeline material of gas gathering manifold of (drip washing) of ammonia, also can change design.The chlorine-containing gas that the thermolysis plastic waste produces is fixed by the drip washing formation ammonium chloride of ammoniacal liquor, and it is harmless to make it to become.
General coal can be divided into the non-little caking coal that is suitable for preparing the caking coal of blast furnace coke and is unsuitable for preparing blast furnace coke, in the coke-fired furnace operation of reality, for the coke quality that obtains stipulating, caking coal is used than mixing as mixing coal with any with non-little caking coal.Here non-little caking coal is meant that generally the highest flow index is below the 10ddpm in the fluidity test of the employing Giesler air blast instrument method of JIS M8801 regulation, or the average reflectance of quiet maceral is the coal below 0.8.To plastic waste is studied with pack into when carrying out thermolysis in the coke-fired furnace ratio of mixture of plastic waste and the relation of coke quality of coal,, also can keep coke quality even the result joins 1wt% with plastic waste.When the addition of plastic raw materials surpassed 1 weight %, coke strenth was to reach balance can fully compensate coke strenth by the proportioning that reduces non-little caking coal, the proportioning that increases caking coal when reducing.
During with coke-fired furnace destructive distillation coal, its temperature is up to 1300 ℃.On the other hand, polyvinyl chloride or polyvinylidene chloride begin thermolysis about 250 ℃, in about 400 ℃ of gasifications, decompose fully at 1300 ℃.Therefore, if with plastic containing chlorine in coke-fired furnace with coal thermolysis or destructive distillation, thermolysis or pyrolysis temperature, pattern can be identical with the former dry distillation of coal.
About the apportioning method of plastic waste in blast furnace and coke-fired furnace, be basically to by the influence of the influence of quality, chlorine, spray into the blast furnace of the upper limit decision amount beyond may treatment capacity and handle with coke-fired furnace and get final product.At this moment, preferably the plastic waste that reclaims is divided into low material and the high material of cl content of cl content that blast furnace is used.Its method is proportion separation method, the manual selection for example.
The proportion separation method is to utilize that the proportion of chlorine-containing resins such as vinylchlorid in the plastic waste or chlorinated organics is high especially to carry out isolating method.The proportion of most of plastics such as polyethylene, polypropylene is 0.90～0.97, the relative proportion of vinylchlorid more greatly 1.16～1.56 therewith, and ABS resin, PET resin are also greater than 1.Therefore, after the plastic waste that will contain vinylchlorid is ground into particulate, for example can makes water carry out proportion and separate.That is to say, make proportion surpass 1 plastic waste sedimentation with settlement separate machine, proportion is lower than 1 plastic waste and discharges with water.To supply with the tilted plate that constitutes by wire netting with the plastic waste that water is discharged, water is separated with plastic waste.The proportion that obtains surpasses chlorine-containing resins or chlorine-containing organic compounds such as containing more vinylchlorid in 1 the plastic waste, and proportion is lower than in 1 the plastic waste vinyl-chloride-containing hardly, and cl content is below 0.5wt%.Representative proportion separation method is the centrifugal proportion tripping device of swing roller for example, can realize by buying commercial device.Density separation also can adopt the air classification method.
In addition, the occasion that treatment capacity is few can be selected to be relatively easy to separate to remove chlorine-containing resins or chlorine-containing organic compounds by manual.This is because the purposes of chlorine-containing resins such as vinylchlorid is relatively limited to, and can easier judge by color or shape.
The mensuration of cl content can adopt the method for following explanation in the plastic waste.The 10kg plastic waste is crushed to about 10～20mm,, finally is divided into 20g/ and criticizes, as representative sample by carrying out quartering repeatedly.With this sample freezing and pulverizing powdered.As way of qualitative analysis, this powder is carried out the per-cent grade analysis by fluorescent x-ary analysis.As quantitative analysis method, by ion-chromatographic determination CI ionic weight, will adopt the chloride conversion that cartridge type CI test method obtains among the JIS-K-2541 " crude oil and petroleum product sulfur test method " is total CI.With the mean value of this result as cl content.
To obtain cl content be plastic waste below the 0.5wt% in order to separate by proportion, can adopt the method for following explanation.(10～20mm) supply with the centrifugal proportion tripping device of swing roller with water with the broken plastic waste of the fine powder of having removed impurity.Cylinder is pulverized plastics because the acceleration (on the separating water surface) of 1000～1700G is divided into seston (lightweight thing) and sediment (heavies) in specific gravity liquid with 2000～3000rpm rotation.Be that 5～10% plastic waste can reclaim lightweight thing 50%～70% by the concentration that contains chlorine during supply, the content of chlorine is 0.3～0.5wt%.This is because the proportion of chlorine-containing resins is more heavy 0.1～0.2 than the ratio of polyethylene, polypropylene, polystyrene foamed, can be used as sediment and separates.
Be discharged into by coke-fired furnace or thermal decomposition furnace and accumulated the ammonium chloride that the chlorine-containing gas that derives from plastic waste in a large number and ammonia react produce in the ammoniacal liquor outside the system, preferably to wherein adding for example sodium hydroxide (caustic soda) of highly basic.Highly basic also can be potassium hydroxide except that sodium hydroxide.Like this, the reaction of ammonium chloride in the ammoniacal liquor and sodium hydroxide generates sodium-chlor and ammonia.The addition of sodium hydroxide is preferably identical with the ammonium chloride equivalent or more.
In order to handle the ammoniacal liquor of discharging, be provided with deamination equipment in the past by coke-fired furnace.In this deamination equipment, after by the steam stripping free ammonia being eliminated, carry out the active sludge treatment discharging.In the present invention, owing to made the ammonium chloride in the ammoniacal liquor form sodium-chlor and ammonia by sodium hydroxide before entering deamination equipment, nitrogen all in the ammoniacal liquor all exist with the form of ammonia.Therefore, with deamination equipment ammonia is eliminated, the result has removed the nitrogen in the ammoniacal liquor.Since only residual in the ammoniacal liquor of from deamination equipment, discharging by harmless sodium-chlor, even directly discharging does not worry that meeting increases the nitrogen in the seawater yet.
Embodiment
(form: combustiblematerials 75% (wherein chlorine is 5～10%) for the plastics that branch away in the average general refuse of from refuse bag, collecting, magneticmetal 5%, aluminium: 2%, inorganic componentss such as glass: 8% (wherein 5% is inorganic components in the combustible component), water: 10%), in order to be used as the blast furnace reductive agent, select-wet type proportion broken to separate-remove moisture through broken bag-magnetic force selection-wind-force with vibration screening-fine powder, the step of drying-granulation obtains granularity: 1～10mm, density: more than the 0.3kg/l, ash content: below 10%, chlorine: the material below 0.5%.Calculating raw material availability is 50～60%.This can not satisfy the viewpoint of recirculation.Further adopting the wet type gravity separation to be reduced to 20～30% high chlorine plastics as heavy plastics (high chlorine plastics) raw material availability can not carry out waste treatment, carries out dechlorination by thermal decomposition process, uses as the blast furnace reductive agent.Though at this moment improved raw material availability, also improved cost.
The plastic waste that contains vinylchlorid is carried out proportion separation or manual the selection, be divided into vinyl-chloride-containing many plastic waste and the few plastic waste of vinyl-chloride-containing, the plastic waste that vinyl-chloride-containing is the many coke-fired furnace of packing into carries out thermal decomposition process, and the embodiment the when plastic waste that content of vinylchloride is few sprays into blast furnace by the air port is as shown in table 1.In addition, the amount of tapping a blast furnace of blast furnace is 10,000 tons of every days.Table 1
Operation evaluation for coke-fired furnace, (150 to change back+150mm) be more than 84 according to the coke rotating cylinder intensity of JIS K2151 by the coke strenth that extrudes in the carbonization chamber after the destructive distillation, in the light oil chloride concentration be below the 10ppm, the chlorine of catching by flushing accounts for more than 90%, and to add caustic soda be that 20mg/l is when following by steam stripped (stripping) except that the concentration of nitrogen in the waste liquid of deammoniation, be zero, though have one when insufficient for *.For the evaluation of blast furnace, not having faults such as furnace top pressure variation, blast furnace stack pressure change in judgement in addition, can obtain the amount of tapping a blast furnace of planning, is zero when operating smoothly.
The operation of embodiment 5 is continued about one month, and the result can handle about 7000 tons plastic waste.
Industrial applicibility
, make the waste plastics that contains chlorine in coke-fired furnace, carry out heat and divide with blast furnace and coke-fired furnace by also Separate and process, can omit the dechlorination step of waste PVC, perhaps waste PVC can not discarded, Even waste PVC is in a large number recycling also.
Claims (12)
1, the treatment process that contains resin or organic compound or both plastic waste, it is characterized in that the part that will contain resin or organic compound or both plastic waste handles as reductive agent in blast furnace, to the remaining all or part of thermal decomposition process of carrying out, the gas that thermolysis is produced contacts with ammoniacal liquor.
2, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 1 is characterized in that ammoniacal liquor produces when the destructive distillation coal.
3, the treatment process that contains resin or organic compound or both plastic waste, a part that it is characterized in that containing resin or organic compound or both plastic waste is handled as reductive agent in blast furnace, all or part ofly carries out thermal decomposition process with coke-fired furnace to remaining.
4, the treatment process that contains resin or organic compound or both plastic waste, it is characterized in that to contain resin or organic compound or both plastic waste and be divided into cl content many material and the few material of cl content, in blast furnace, handle the few material of cl content, in coke-fired furnace, the high material of cl content is heat-treated.
5, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 4 is characterized in that will contain resin or organic compound or both plastic waste by the proportion separation is divided into cl content many material and the few material of cl content.
6, contain resin or organic compound or both Treatment of Waste Plastics methods, it is characterized in that to contain resin or organic compound or both plastic waste and be divided into above material of cl content average out to 0.5wt% and the following material of cl content average out to 0.5wt%, in blast furnace, handle the material below the cl content average out to 0.5wt%, the material more than the cl content average out to 0.5wt% is carried out thermal decomposition process in coke-fired furnace.
7, contain resin or organic compound or both Treatment of Waste Plastics methods, after it is characterized in that to contain resin or organic compound or both plastic waste parts and carrying out dechlorination in advance and handle, in blast furnace, handle as reductive agent, for the remaining all or part of dechlorination processing of not carrying out in advance, carry out thermal decomposition process simultaneously with coke-fired furnace.
8, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 7, it is characterized in that containing resin or organic compound or both plastic waste parts and carry out dechlorination in advance and handle the content of chlorine is reached below the 0.5wt%, in blast furnace, handle then as reductive agent.
9, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 8, it is characterized in that to contain resin or organic compound or both plastic waste and carry out dechlorination in advance and handle cl content is reached below the 0.5wt%, handle the product of the above-mentioned prior processing of 0.5kg～10kg then with respect to 1 ton of molten iron with blast furnace.
10, the treatment process that contains resin or organic compound or both plastic waste, it is characterized in that containing resin or organic compound or both plastic waste parts and directly do not handle as reductive agent in blast furnace except that dechlorination in advance, the remaining all or part of dechlorination that do not remove in advance carries out thermal decomposition process in coke-fired furnace.
11, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 10, it is characterized in that with per 1 ton of molten iron 0.5kg as lower limit, with the blast furnace treatment capacity of considering the chlorine permissibility is the upper limit, will contain resin or organic compound or both plastic waste and not remove dechlorination in advance and directly handle as reductive agent in blast furnace.
12, the treatment process that contains resin or organic compound or both plastic waste as claimed in claim 11 is characterized in that not removing dechlorination in advance and directly handling in blast furnace containing resin or organic compound or both plastic waste below the above 1.7kg of 0.5kg with respect to 1 ton of molten iron.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24406998 | 1998-08-28 | ||
| JP244069/1998 | 1998-08-28 | ||
| JP132091/1999 | 1999-05-13 | ||
| JP13209199A JP3095739B2 (en) | 1998-08-28 | 1999-05-13 | Processing method of resin or organic compound or waste plastic containing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1286715A true CN1286715A (en) | 2001-03-07 |
| CN1198868C CN1198868C (en) | 2005-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998016462A Expired - Lifetime CN1198868C (en) | 1998-08-28 | 1999-08-27 | Method of treating resin or organic compound, or waste plastics contg. them |
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| Country | Link |
|---|---|
| US (1) | US6436168B1 (en) |
| EP (1) | EP1029889B1 (en) |
| JP (1) | JP3095739B2 (en) |
| KR (1) | KR100385154B1 (en) |
| CN (1) | CN1198868C (en) |
| AU (1) | AU5445099A (en) |
| CA (1) | CA2308710C (en) |
| ES (1) | ES2372019T3 (en) |
| TW (1) | TW506981B (en) |
| WO (1) | WO2000012599A1 (en) |
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| CN105426786A (en) * | 2015-11-11 | 2016-03-23 | 清华大学 | Data encryption/decryption method and system based on racetrack memory |
| CN108424804A (en) * | 2018-02-13 | 2018-08-21 | 鞍钢股份有限公司 | A kind of method of efficient process solid waste ion exchange resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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- 1999-05-13 JP JP13209199A patent/JP3095739B2/en not_active Expired - Lifetime
- 1999-08-27 CN CNB998016462A patent/CN1198868C/en not_active Expired - Lifetime
- 1999-08-27 US US09/530,330 patent/US6436168B1/en not_active Expired - Lifetime
- 1999-08-27 TW TW88114878A patent/TW506981B/en not_active IP Right Cessation
- 1999-08-27 AU AU54450/99A patent/AU5445099A/en not_active Abandoned
- 1999-08-27 WO PCT/JP1999/004654 patent/WO2000012599A1/en active IP Right Grant
- 1999-08-27 CA CA002308710A patent/CA2308710C/en not_active Expired - Lifetime
- 1999-08-27 EP EP19990940539 patent/EP1029889B1/en not_active Expired - Lifetime
- 1999-08-27 ES ES99940539T patent/ES2372019T3/en not_active Expired - Lifetime
- 1999-08-27 KR KR10-2000-7004548A patent/KR100385154B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105426786A (en) * | 2015-11-11 | 2016-03-23 | 清华大学 | Data encryption/decryption method and system based on racetrack memory |
| CN108424804A (en) * | 2018-02-13 | 2018-08-21 | 鞍钢股份有限公司 | A kind of method of efficient process solid waste ion exchange resin |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1029889B1 (en) | 2011-10-12 |
| WO2000012599A9 (en) | 2000-06-02 |
| KR20010031507A (en) | 2001-04-16 |
| KR100385154B1 (en) | 2003-05-22 |
| CA2308710C (en) | 2004-01-27 |
| AU5445099A (en) | 2000-03-21 |
| US6436168B1 (en) | 2002-08-20 |
| JP2000136393A (en) | 2000-05-16 |
| EP1029889A4 (en) | 2009-11-04 |
| JP3095739B2 (en) | 2000-10-10 |
| WO2000012599A1 (en) | 2000-03-09 |
| TW506981B (en) | 2002-10-21 |
| ES2372019T3 (en) | 2012-01-13 |
| CA2308710A1 (en) | 2000-03-09 |
| CN1198868C (en) | 2005-04-27 |
| EP1029889A1 (en) | 2000-08-23 |
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